Detection of glycolates

ABSTRACT

A composition of matter for detecting glycolate incapacitating chemical agents; the composition of matter having the generic formula   WHEREIN R is an amino or imino group, the glycolate agents having the generic formula   WHEREIN R, R1, and R11 are each any aromatic group, any aliphatic group, any substituted aromatic group, any substituted aliphatic group, any cyclo aliphatic group, any cyclo aliphatic group having nitrogen in the cyclic structure, and any combinations thereof.

United States Patent [191 Crabtree et al.

[451 Sept. 2, 1975 [54] Z-DIPHENYLACETYL-l,3-INDANDIONE DERIVATIVES [75] Inventors: Eleanor V. Crabtree, Towson;

Edward J. Poziomek, Bel Air, both of Md.

[73] Assignee: The United States of America as represented by the Secretary of the Army, Washington, DC.

[22] Filed: Mar. 23, 1972 [21] Appl. No.: 238,711

Related US. Application Data [63] Continuation of Ser. No. 854,811, Aug. 29, 1969,

abandoned.

[52] US. Cl. 260/240 G; 23/230; 252/408;

260/566 B [51] Int. Cl. C07d 31/22; C076 119/10 [58] Field of Search 260/566 B, 240 G Mosher et al., Talanta, Vol. 15, pp. 482-484, (1968), QD71T3.

Primary ExaminerLeland A. Sebastian Attorney, Agent, or FirmNathan Edelberg; Robert P. Gibson; Kenneth P. Van Wyck [57] ABSTRACT A composition of matter for detecting glycolate incapacitating chemical agents; the composition of matter having the generic-formula wherein R is an amino or imino group, the glycolate agents having the generic formula wherein R, R, and R are each any aromatic group,-

any aliphatic group, any substituted aromatic group, any substituted aliphatic group, any cyclo aliphatic group, any cyclo aliphatic group having nitrogen in the cyclic structure, and any combinations thereof.

1 Claim, No Drawings a Z-DIPHENYLACETYL-1,3-INDANDIONE DERIVATIVES DEDICATORY CLAUSE The invention described herein may be manufactured, used, and licensed by or for the Government for governmental purposes without the payment to us of any royalty thereon.

This is a continuation of application Ser. No. 85481 1, filed Aug. 29, 1969, now abandoned.

Our invention relates to a composition of matter used to detect glycolate incapacitating chemical agents.

Since glycolate incapacitating agents act on the autonomic parasympathetic and central nervous system, to interfere with transmission of impulses along a nerve or from nerve fibers to muscle fibers or secretory cells or from one nerve fiber to another across synapses in ganglia, and produce incapacitating physiological effects, a need exists to detect the presence of such glycolate agents in the atmosphere; such as could be encountered in field conditions during warfare. The prior art detection techniques of glycolates were based on chemical reactions, but, due to the lack of chemical reactivity of the glycolates, prior art chemical reaction techniques were not successful and did not solve the glycolate detection problem due to the complexity of the chemical reactions, lack of detection specificity, and lack of detection sensitivity. Our invention was conceived and reduced to practice to overcome the aforementioned prior art problems and to satisfy the long felt need for a relatively simple, easy to use, and sensitive means to detect glycolate agents with specificity.

A principal object of our invention is to provide a means which will detect all glycolate incapacitating agents and which is a sensitive detection means.

Another object of our invention is to provide a means which will detect all glycolate incapacitating agents and which is relatively simple and easy to use to provide de tection specificity.

Other objects of our invention will be obvious or will appear from the specification hereinafter set forth.

Our invention involves compositions of matter as glycolate chemical incapacitating agent detection means which are represented by the generic formula as follows:

wherein R is any amino or imino group such as NH NHCH NHCOC,;H,-,, NHCOOC H N=CHN(C H N=C(CH (CH NC H JCI, and N(COC H The compositions of matter of our invention are made by conventional methodology, such as disclosed in the publication TALANTA, 1968, vol. 15, pp. 482 to 484, Pergamon Press.

The glycolate agents which the above defined composition of matter will detect are represented by the generic formula as follows:

O O 1 l u R-C-C-OR wherein R, R, and R are any aromatic group, any aliphatic group, any substituted aromatic group, any substituted aliphatic group, any cyclo aliphatic group, and any cyclo aliphatic group having nitrogen in the cyclic structure. R, R, and R can each be the same member of the aforementioned groups, or any combination of the aforementioned groups can be selected for R, R, and R.

The compositions of matter used as our detection means can all be prepared in the same manner as set forth in the exemplary procedures as follows.

EXAMPLE 1 A mixture of l .75 grams of pdimethylaminocinnamaldehyde and 2.92 grams of 2- diphenylacetyl- 1 3-indandione-1 -hydrazone was stirred to produce a homogeneous mixture and refluxed in 50 ml of chloroform for 20 minutes; two drops of concentrated HCl being added to the reflux mixture prior to refluxing to act as a catalyst. A red solution was produced which was filtered hot to remove any unreacted starting materials. The filtered solution was cooled to room temperature and -200 ml of anhydrous ether was added which produced a red precipitate. The precipitate was removed from the solution through filtration and recrystallized from 50 ml of a boiling methanol-chloroform (10:1) mixture which yielded 4.61 grams of a brick red solid, 2- diphenylacetyll 3-indandionel -p-dimethylaminocinnamaldazine, having a melting point of 198C.

Percent analysis for C H N O Calcd: C, 79.8; H, 5.7; N, 8.2; O, 6.3.

Found: C, 79.9; H, 5.7; N, 8.5; O, 6.2.

EXAMPLE 2 A mixture of 2.50 grams of N-methiodide-4-pyridine carboxaldehyde and 2.92 grams of 2-diphenylacetyl-l 3-indandionel -hydrazone was stirred to produce a homogeneous mixture and refluxed in 50 ml of chloroform for thirty minutes; two drops of concentrated HCl being added to the reflux mixture, prior to refluxing, to act as a catalyst. The refluxed solution was cooled to room temperature, and a brownish orange product began to precipitate on cooling. After cooling to room temperature, 100-200 ml of anhydrous ether was added, and a brownish orange product precipitated. The product was extracted with 50 ml of a hot methanolchloroform (10:1) mixture. After filtering the mixture while hot, 4.65 grams of a brownish orange solid, Z-diphenylacetyl- 1 3-indandionel -p-N- methiodidepyridine carboxaldazine was obtained 5 which had a melting point of 230C.

The efficacy of all of the compositions utilized in our technique were tested as shown in the following exemplary procedure.

EXAMPLE 3 milligrams of detection composition means 2- diphenylacetyl-l 3-indandionel -p-N methiodidepyridine carboxaldazine was dissolved in 10 milliliters of tetrahydrofuran acidified with 23 drops of concentrated HCl. Glycolate incapacitating chemical agent was spotted as an ethanolic solution on the grid side of a conventional Gelman glass microfiber sheet. The detection composition means was sprayed as a very fine mist onto the glycolate spotted grid side. Upon viewing the microfiber sheet, as soon as the solvent had volatilized (1-2 minutes), under either long or short wave ultra violet light, the long wave being generally more sensitive, yellow fluorescent spots were visible which demonstrated the presence of glycolate incapacitating agent. As a result of out testing, we determined that the presence of as little as 0.1 micrograms of glycolate incapacitating agent can be detected by our method. The detection composition can be sprayed by either a Freon propelled spray can or by an air driven spray; both spray techniques being those as conventionally used in thin layer chromatography. In the case of the Freon spray can, a three ounce can was used which contained grams of the detection composition of our invention, 40 grams of trichloromonofluoromethane, and 40 grams of dichlorodifluoromethane.

EXAMPLE 4 10 milligrams of detection composition means 2- diphenylacetyll 3-indandionel -p-dimethylaminocinnamaldazine was dissolved in 30 milliliters of glacial acetic acid to which 0.65 ml of concentrated HCl was added. Glycolate incapacitating chemical agent was spotted as an ethanolic solution on the grid side of a conventional Gelman glass microfiber sheet. The detection composition means was sprayed onto the glycolate spotted grid side as described in Example 3. The microfiber sheet was viewed with ultra violet light, as in Example 3, and a reddish-orange fluorescence was visible which demonstrated the presence of glycolate incapacitating agent.

Test results showed our glycolate agent detection technique to have an absolute sensitivity of 0.1,ug, and temperature has little perceptible effect on the intensity of fluorescence in the range of C to C. Chromatographic and spectroscopic tests substantiated that the fluorescent emission in our technique is due to a weak association of molecules rather than a very fast chemical reaction.

While the glycolate incapacitating agent was sprayed on for test purposes, samples can be collected on any substrate and by any conventional sampling means to be tested by our technique and detection compositions for the presence of glycolate agent. Also, while we utilized acidified tetrahydrofuran and acetic/l-lCl acid as solvents, it is readily apparent that a variety of equivalent solvent systems based on other aqueous and/or organic solvents with suitable acids would be obvious to one of ordinary skill in the art.

We wish it to be understood that we do not desire to be limited to the exact details shown and described, for obvious modifications will occur to a person skilled in the art.

We claim:

1. A compound for use in detecting glycolate compounds selected from the group consisting of 2- diphenylacetyl-l ,3-indandionel-p-dimethylaminocinnamaldazine and Z-diphenylacetyl 1,3-indandione-l-p- N-methiodidepyridine carboxaldazine. 

1. A COMPOUND FOR USE IN DETECTING GLYCOLATE COMPOUNDS SELECTED FROM THE GROUP CONSISTING OF 2-DIPHENYLACETYL-1,3INDANDIONE-1-P-DIMETHYLAMINOCINNAMALDAZINE AND 2DIPHENYLACETYL 1,3-INDANDIONE-1-P-N-METHIODIDEPYRIDINE CARBOXALDAZINE. 